The relationship between microstructure evolution and coefficient of thermal expansion (CTE) of 7A09 aluinum alloy was investigated in this paper. Differential scanning calorimetry (DSC) was combined with transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) to investigate microstructure evolution taking place in 7A09 aluminum alloy during heating and cooling process. The corresponding CTE curves of the 7A09 alloy were recorded by thermal dilatometer. Results indicated that GPII zones and η' phase were main precipitates in the highest strength tempered (T6) 7A09 alloy. The η phase was the main participate in 7A09 alloy during the cooling process. The nonlinear dependency existed between CTE and temperature in both changing temperature processes. During the heating process, obvious additional contraction of alloy volume was directly caused by phase transition, such as dissolution of ´0 phase, transition from η' to η phase and dissolution of η phase. The additional contraction could slow down the increase of CTE greatly and be expressed in the nonlinearity of CTE curve. Volume and energy changes of alloy system influenced the variation trend of CTE directly, which was caused by the precipitation of ´ phase during the cooling process. These effects were revealed by the corresponding nonlinear change of CTE.